TW544735B - Semiconductor device having a high-dielectric gate insulation film and fabrication process thereof - Google Patents

Abstract

An ultra high-speed semiconductor device has a high-K dielectric gate insulator layer, wherein spread of impurities to a Si substrate from a gate electrode through the high-K dielectric gate insulator layer, and spread of oxygen and metallic elements from the high-K dielectric gate insulator layer to the Si substrate or the gate electrode are suppressed by arranging the high-K dielectric film sandwiched by nitrogen atomic layers on the Si substrate that is covered by an oxygen atomic layer.

Description

544735 V. Description of the invention The paper size is suitable for wealth management (CNS) M specification (MW public) A7 B7 The related application is based on the Japanese priority application No. 200b 097128, and the application date is 2001 On March 29, and the application date of 2000-77705, March ^ 2002, a case was filed with the Japan Patent Office, the entire contents of which are incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to semiconductor devices, and more particularly, to semiconductor devices having high-k dielectric films made of metal oxides or metal silicates, and methods of making the same. 2 _Related technical description Because semiconductor integrated circuit elements such as CMOS LSI are required for ultra-high-speed operation, this element is composed of an extremely short gate length < electric field effect transistor (MOSFET). In order to achieve ultra-high-speed operation, intensive research has been conducted on its miniaturization. " When the MOSFET is miniaturized, it is also required to thin the gate insulating film. For example, it is expressed by the oxide equivalent thickness, and it is required to reduce the film thickness of the gate insulating film to about 2.5 nm or less. It is known that Shi Xi oxide with excellent leakage characteristics and small interface step density is used as the gate insulating film of MOSFET. However, the conventional insulating film made of sand oxide has the following problems. As the physical thickness of the gate insulating film becomes thinner, the direct plutonium current increases. Any film thickness smaller than the aforementioned value will cause the biggest problem of gate leakage current due to direct penetration of the barrier current. If the gate leakage current increases, the actual leakage current will keep flowing during the gate closing period, which will cause, for example, operation 4 (Please read the precautions on the back before filling this page)

) 44735 A7 ^ ---------------- B7 V. Description of the Invention (2) Problems such as abnormal operation and high power consumption. To solve these problems, high-K dielectric films such as metal oxides and metal silicates have been studied. In the present invention, a high-k dielectric film is used to privately display a dielectric film having a specific dielectric constant of 10 or more. However, in the case of high-K dielectric interlayer films using metal oxides or metal silicates, the problem of unstable MOSFET operation occurs. The reason for the unstable operation of MOSFETs is that the gate-doped boron penetrates into the high-κ dielectric gate insulating film. , Hydrogen in the gas used in the process attacks the high-κ dielectric gate insulation film and other phenomena. When a gate structure containing a high-K dielectric gate insulating film is formed on the surface of the silicon substrate, at the interface between the silicon substrate and the high-K dielectric gate insulating film, or between the high-k dielectric gate insulating film and the polycrystalline silicon gate. Interface reactions may occur, such as metal silicide formation reactions. The research on the high-k dielectric gate insulation film has been mainly conducted on the suppression of the direct penetrating barrier current, but has not thoroughly studied the stability of the device characteristics. For example, JP, 2001-267566 discloses a gate insulating layer, which is formed by depositing a first silicon nitride molecular layer on the surface of a silicon substrate by a so-called monoatomic layer deposition (atomic layer CVD) method; a high-k dielectric layer such as The zirconia layer is formed on the silicon nitride molecular layer by repeatedly forming an oxygen atom layer and a hafnium atom layer, and the oxygen atom layer and the interatomic layer are individually formed by an atomic layer CVD method; and a second silicon nitride molecular layer This layer is formed on a high κ ”cladding layer by the atomic layer CVD method. In addition, the related art also discloses a gate insulating layer formed on the surface of a silicon substrate by the so-called monoatomic layer deposition (atomic layer CVD) method. Composed of the first silicon dioxide molecular layer; a high-k dielectric layer such as yttrium oxide; the paper size is toward the family standard (CNS) M specification ⑵⑽297 public love) ----- (Please read the back Attention ^ Fill in this page again}. Order 丨 544735 A7 '^ ----- 一 —__ B7 ^ _ V. Description of the invention ~'-It is formed on the molecular layer of rat fossil, which is formed by repeated formation of oxygen atoms Layer and source = layers (each formed by an atomic layer CVD method); and The silicon oxide knife layer is formed on the high-k dielectric layer by the atomic layer CVD method. For example, the uranium is described; the I-gate insulation film has a small oxide equivalent thickness, and when applied to a substrate with a gate length of 01 microns or less In high-speed semiconductor devices, it is possible to effectively suppress the indirect leakage current caused by the direct penetration barrier effect. The first and second silicon nitride molecular layers in the silicon, silicon, and silicon structures are sandwiched by high-K dielectric thin films. The valence difference between the two, the surface of the silicon substrate can not be uniformly and completely covered by nitrogen atoms, but inevitably appear dangling bonds. If the dangling bonds appear in the gate insulation film, especially with the surface of the silicon substrate (as a channel area) The gate insulation film at the interface changes the threshold characteristics of the semiconductor element by carrier breakdown. In the example of the previous technique, the high-k dielectric film is vertically sandwiched by a pair of silicon dioxide molecular layers. There is no dangling bond formed at the interface between the silicon substrate and the gate insulating film. However, a problem arises because the gate insulating film does not have a nitrogen atomic layer. The threshold characteristic of the second substrate 'semiconductor device changes. In addition, in this kind of high κ dielectric gate insulation film that lacks a nitrogen atom layer, the oxygen chaos of the high κ dielectric film easily reaches the silicon substrate by diffusion, causing the channel area. The problem of poor carrier mobility is caused. In addition, it also causes the problem of metal elements from diffusing from the gate insulating film to the Shixi substrate. The metal elements that reach the silicon substrate cause, for example, metal silicide formation reactions. Such a high-k dielectric The gate insulation film has the following problems, including the basic paper size of Shi Xi_Family Standard (CNS) Α4 size (2K) × 297M) 6 ----------- · installation 丨 (Please read the Note for this page, please fill in this page), τ 544735 V. Description of the invention (4) (Please read the notes on the back before filling this page) Board = High [Problem of forming dangling bonds at the interface of the dielectric gate insulation barrier, and the number of impurities The problem of infiltration through the high-K dielectric gate insulation film. In addition, the diffusion of oxygen and metals has not been resolved. Thus, even when the semiconductor element is manufactured using a high dielectric gate insulating film, the excellent effects expected from a high-K dielectric gate insulating film cannot be achieved. Thus, the general purpose of the present invention is to provide semiconductor devices for financial purposes, in which the aforementioned problems can be eliminated. The third and more specific purposes of this month are to provide a half-knife element with a high-K 7 gate insulation film and a method for manufacturing the same. The problem of penetration is eliminated, and the reducing atmosphere contained in the gas used in the manufacture of the element, such as The problem of changing element characteristics caused by chlorine gas can be successfully solved, as well as inhibiting the reaction between the high-K dielectric gate insulating film and the Shixi substrate, and the reaction between the 咼 K dielectric gate insulating film and the gate. . Another objective of the present month is to provide a semiconductor device including: a channel region formed in a silicon crystal layer, and a gate insulating film formed in the channel region, containing a silicon oxide layer formed on a stone evening crystal layer -A first nitride stone layer formed on the oxide stone layer, a dielectric metal oxide layer formed on the first silicon nitride layer, and a second nitrogen layer formed on the dielectric metal oxide layer A silicon layer and a gate are formed on the gate insulating film. Another objective of this month is to provide a semiconductor device including: a silicon substrate, a gate insulating film formed on the silicon substrate; and

544735 V. Description of the invention (a formed on the closed insulating film, the closed electrode 'wherein the open insulating film contains: younger brother,% margin skin, which contains a milk atom composed of oxygen atoms s each oxygen atom system &-child Layer, the Shixi atomic layer, each Shixi atomic system is bonded to the oxygen source, and-=: Ca_sublayer ", is bonded to the nitrogen atom of the nitrogen atomic layer /-Shixi atom The first and% edge film of each Shixi atom, which contains an oxygen composed of oxygen atoms, and each oxygen atom system is bonded to the Shixi atom of the second Shixi atomic layer;-a metal atom composed of all the atoms Layer, each metal atom system and the oxygen atom layer oxygen bond; the oxygen atom layer composed of oxygen atoms, each oxygen atom system and = 2 sub-bonds; and at the top '-composed of oxygen atoms : =, One metal of each oxygen atom system and metal atom layer> -The third insulating film 'comprises a silicon atom layer composed of silicon atoms, and this layer covers each of the topmost oxygen atom layers' -An oxygen atom bond to the topmost oxygen family; and-a nitrogen source consisting of nitrogen atoms Layer, each nitrogen atom system and the topmost oxygen atom layer and the dream atom layer are bonded to each other. Another object of the present invention is to provide a method for manufacturing a semiconductor, including: a process in which gas radon is supplied to the surface of a cutting substrate, Let the surface of the Shixi substrate absorb silicon molecules of a single molecular thickness, in which the oxygen-containing gas is supplied to the surface of the Shixi substrate, and this surface applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 544735 A7 B7 on this paper scale V. Description of the invention (6) _ After the process (A) absorbs silicon atoms, the adsorbed silicon molecules are oxidized, and a stone oxide molecular layer is generated on the surface of the stone substrate. (C) A process in which gas phase silicon is supplied. The surface of the silicon substrate is covered by a layer of silicon oxide molecules after the process (B), so the silicon molecules are absorbed to a single molecular thickness, (D) —the process, in which a nitrogen-containing gas is supplied to the surface of the silicon substrate, and the surface is in the process ( C) The silicon molecules are then adsorbed, so that the adsorbed silicon molecules form a silicon nitride molecular layer on the surface of the silicon substrate. (E) — the process in which oxygen-containing gas and metal element-containing gas are alternately supplied The surface of the silicon substrate, which is covered by a silicon nitride molecular layer after the process (D), thereby forming a dielectric metal oxide film. (F)-Process' wherein the gas phase silicon is supplied to the surface of the substrate, and the surface is on the process (E) ) Later, it needs to be covered by a dielectric metal oxide film, so silicon molecules are adsorbed to a single molecular thickness to form a silicon molecular layer, and (G) 'process' where a nitrogen-containing gas is supplied to the surface of the substrate, and this surface is used for manufacturing (F) It is then covered by a silicon molecular layer, so the adsorbed silicon molecules form a nitride stone molecular layer on the surface of the silicon substrate. The features and advantages of the present invention are described in the following description, and part of the description and the drawings will be self-explanatory, or may be It is learned from the practice of the present invention according to the teaching provided in the description. The objects and other features and advantages of the present invention can be achieved and achieved through a semiconductor element and a method for manufacturing the same, which are particularly complete, clear, specific, and exact terms It is stated in the description that a person skilled in the art can implement the present invention. This paper size applies to China National Standard (CNS) A4 specifications (210 > < 297 public love) 9 (Please read the precautions on the back before filling in this page)

544735 A7 ____B7 V. Description of the invention (7) " ~ A brief description of star A Figure 1A-Figure ij is a schematic diagram _ shows a method of manufacturing a semiconductor element according to the first specific embodiment of the present invention; Figure 2 is The sketch shows a sample structure made from the structure in Figure u, which is used to measure the leakage current. Figure 3 shows the characteristics of the leakage current in the thumbnail. The nitrogen atomic layer in Figure 2 is not formed in Figure 2. Fig. 4 is a schematic diagram showing the characteristics of the gate leakage current. Here, Fig. 1 is a sample in which the nitrogen atom layer is formed in Fig. 2. Figs. 5 A-5 G are schematic diagrams showing a second example according to the present invention. DETAILED DESCRIPTION A method of manufacturing a semiconductor device; and FIG. 6 is a schematic view showing a structure of a CMOS semiconductor device according to a third embodiment of the present invention. Description Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. Figures 1A to 1J show a first embodiment of the present invention, a method for manufacturing a high-K dielectric gate insulating film on a silicon substrate ^. Although a pure dielectric gate insulating film is made by an atomic layer deposition method in the following description, for example, a high-k dielectric gate insulating film may be made by the MBE method or the like. mία diagram, after removing the natural oxide film on the surface of Shi Xiji to expose the silicon atoms on the substrate surface, H2O (water vapor) is typically supplied at 300 substrate temperature. In the process of FIG. 1B, water Molecules are adsorbed on the surface of the Shi Xi substrate 1. 4 Results The surface of the Shixi substrate was uniformly-covered by a single-atom-thick oxygen atom layer. In this case, one of the oxygen atoms of the oxygen atomic layer 0L1. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210x297 cm) 10 Binding ---- ^^-line · C Please read the note on the back first Please fill in this page again} The bond of the bond system substrate and the other of the oxygen atom—the bond bond wind atom. As a result, on the surface of the dream substrate 1, a molecular oxide oxidized oxidized layer of ^ 2 oxidized oxidized molecular layer surface 2 was covered with 0H. Although the oxygen atomic layer is not an atomic thickness, 9G% or more oxygen atomic bond = the pair of atoms on the substrate surface, so it can be regarded as the thickness of the monoatomic layer. . Secondly, on the surface of the structure shown in FIG. 1B of the tetrachloro-cut gas supply substrate temperature 400 C in the process of lc®, silicon tetrachloride molecules are adsorbed. In this case, 'the hydrogen atom based on 0H on the surface of the oxygen atom layer 0Ll reacts with the tetrachloride stone molecule and is removed in the form of hydrogen chloride'. As a result, the surface of the silicon substrate has a single-atomic thickness from the stone layer atom SL1. -cover. In this way, the two bond bonds of the cut atom # SL 1 and the oxygen atom layer are called two oxygen atom bond society, and the other two bonds of Shi Xi atom are bonded with two chlorine atoms. Although strictly speaking, the Shi Xi atomic layer SL i may not be a single atom thickness, but 90% or more of the silicon atoms are bonded to the oxygen atoms of the-oxygen atom layer OL, which is subsequently regarded as a single atomic layer. In the process of 1D map, ammonia gas at the substrate temperature of 4001: supplied to the structure surface of the ic map, and then the single-atom-thickness nitrogen layer is formed by the chlorine atoms that are attributed to the various atoms of the dream atom layer through α. In this case, the chlorine atom of the silicon atom of the silicon atom layer SL! Which is first bonded is removed as hydrogen chloride. Each of the nitrogen atoms formed in this manner is bonded to a hydrogen atom with two unbonded silicon atoms. Through the process of FIG. 10, the single-atom-thickness nitrogen cut layer 3 is formed on the single-atom-thickness dioxon molecular layer ^. Although «the nitrogen atomic layer NLi is not mono-atomic in thickness, it is said to be%. 5. The description of the invention (9) or above The corresponding atom of nitrogen atom bonded to the hard atomic layer SL i can be regarded as a single atom in essence. Thick layer. ,,. Secondly, the silicon tetrachloride molecules are uniformly adsorbed on the surface of the structure shown in FIG. 1D of the 1C process of tetrachloro gas supply substrate temperature 400C. In this case, a chlorine atom bonded to a nitrogen atom called a nitrogen atom layer is removed as hydrogen chloride. As a result, the surface of the nitrogen atom layer NLi is uniformly covered by the silicon atom layer SL2 having a single atom thickness. In this way, the two bonds of one stone atom in the formed silicon atomic layer 乩 2 are individually bonded to one nitrogen atom of the nitrogen atomic layer. The remaining two bonds of the silicon atom in the silicon nitride molecular layer are each bonded to a chlorine atom. Although strictly speaking, the Shixi Atomic Layer SL2 is not a single-atom thickness, but 90% or more of the silicon atom system and the corresponding nitrogen atom of the nitrogen atom layer NL1 are bonded, which can actually be regarded as a thickness layer of the unit. Secondly, in the process of FIG. 1F, water vapor (private) is supplied to the structure surface of FIG. 1E at a substrate temperature of 400. Then the chlorine atom bonded to the silicon atom of the silicon atom layer SL is removed in the form of hydrogen chloride to form an oxygen atom layer 0 ", wherein the oxygen atom system is bonded to the silicon atom of the silicon atom layer St. The oxygen of the oxygen atom layer The atoms and silicon atoms of the silicon atom layer SL2 can be regarded as constituting a silicon dioxide monomolecular layer or a part of a high-K dielectric film, which will be described later. Each hydrogen atom system and oxygen atom layer 〇L2 An oxygen atom is bonded to form a 0H base. Although strictly speaking, the oxygen atom layer is not a single-atom thickness, but because 90% or more of the oxygen atom system is bonded to the silicon atom of the silicon atom layer sl, it can be seen from above. It is an early atomic thickness layer. In the process of FIG. 1G, thorium tetrachloride gas is supplied to the surface of the structure of the graph, and thorium tetrachloride molecules are uniformly adsorbed on the oxygen atom layer OL2. In this case 544735 A7 ---- ------ B7 _ 5. In the description of the invention (10), the hydrogen atom forming a 0H base on the surface of the milk atom layer OL2 reacts with the tetrachloride donor molecule, and the hydrogen hydrogen chloride form is removed. As a result, the oxygen atom layer is deposited. 2 is covered by a single atomic layer thickness of the donor atomic layer HL1. The two bonds of one plutonium atom in the sub-layer HL1 are bonded to two oxygen atoms in the oxygen atom layer 0L2, and the other two bonds are individually bonded to one chlorine atom. Although strictly speaking, the plutonium atomic layer has a non-monoatomic thickness. However, since 90% or more of the fluorene atomic system of the fluorene atomic layer is bonded to the corresponding oxygen atom of the oxygen atomic layer 0, the fluorene atomic layer 1 ^ 1 ^ can be considered as a single atom thickness. Secondly, in the process of FIG. 1H, water vapor (h2O) is supplied to the structure surface of FIG. 1G according to the substrate temperature of 400 ° C. As a result, the chlorine atoms of the 铪 atomic layer of the 铪 atomic layer were removed in the form of hydrogen chloride, forming an oxygen atom layer 〇1 ^, which was bonded to the 铪 atomic layer Η by the oxygen atom.铪 of atomic composition. The oxygen atomic layer of the oxygen atom layer 103 forms a monolayer of europium dioxide with the europium atom of the europium layer. In addition, one hydrogen atom binds each oxygen atom of the oxygen atom layer OL3 to form an OH base. And oxygen atom layer ο. Among them, 90% or more of the oxygen atoms are bonded to the corresponding plutonium atoms of the plutonium atomic layer HL, which can be substantially regarded as constituting a single-atom thick layer. The processes of Figures 1G and 1H can be repeated any number of times in the process of Figure π. Therefore, the hafnium dioxide layer 4 that constitutes the oxygen atom layer OL3 and the hafnium atom layer Hl2 is formed on the hafnium dioxide monolayer and the oxygen atom layer. L4 is further formed on the rhenium atomic layer HL2. Although the oxygen atomic layer 103 and the europium atomic layer HL2 are not strictly single-atom-thick, they can be considered substantially as single-atom-thickness layers. In the process of FIG. 1J, silicon tetrachloride gas and ammonia gas are supplied one by one to the structure of FIG. Π. The silicon nitride layer composed of the silicon atomic layer SL3 and the nitrogen atomic layer NL2 * .......... ..... 丨 丨 This paper is a standard size paper towel (CNS) A4 (21GX297)-~ 13 ~ "

..... Packing ..... (Please read the precautions on the back before filling in this page), τ · --line 丨 544735 A7 -------__ V. Description of the invention (11) Atom The layer 5 is formed on the oxygen atom layer 01 ^. Although the silicon atomic layer 81 ^ and the nitrogen atomic layer NL2 are not strictly the thickness layer of the unit, they are similar to the previous atomic layers 0L1 to 0 "and can be regarded as the single-atom-thickness layer substantially. The processes of Figs. 1A to ij The atomic layer OLi measured to the thickness of the atomic layer NL2 is from 15 to 15 nanometers, and a high-scale dielectric gate insulating film is manufactured, and a gate electrode such as a polycrystalline silicon gate is formed thereon.% Figure 1A to 1J In the process of the drawing, especially in FIG. 1A, here the surface of the broken substrate is directly bonded to the interface by the oxygen atom layer 0Ll, or the interface step is formed at the interface to form a high-quality dioxide dioxide single layer | $ 2. So, When the semiconductor device is operated and carriers are transported at a high speed in the channel region, the carriers will not be captured by the dangling bonds and the interface |. Therefore, the threshold characteristics and leakage current characteristics of the semiconductor device will not age. Also because of the manufacturing process of Figure 1D In the process, nitride monolithic layer 3 is formed on silicon dioxide monomolecular layer 2. When the hafnium dioxide is formed on this silicon nitride layer 3 in the process of FIG. 1G to FIG. II, the The hafnium oxide layer and the oxygen-developed Shixi substrate. Further use of this structure Because the nitrogen atom layer of the nitride monolayer is separated from the surface of the stone base with the oxygen atom layer 0Ll and the stone base atom%, it can prevent the threshold characteristics of the semiconductor device due to the fixed charge of the nitrogen atom. In the same way, in this specific embodiment, 'the nitrogen atom NL2 of the nitrogen-containing molecular layer is formed on the dioxide supply layer', so it can effectively suppress the secretion of atoms and oxygen atoms from the hafnium dioxide layer to the polycrystalline stone. Evening poles. In addition, it can also effectively inhibit the dopant dopant from spreading from polycrystalline silicon gates to the hair substrate. For high κ dielectric gate insulating films with the structure shown in Figure 1J, it is important to use this paper size China National Standard (CNS) Α4 Specification (210 × 297)

Installation ---- (Please read the precautions on the back before filling this page) Order --- line 丨 544735 V. Description of the invention (l2 A high-k dielectric film composed of an emulsified layer is composed of an oxygen atom layer. 〇〇 l4 is misplaced. Therefore, each fluorene atom is bonded to four oxygen atoms, and the dimensional fluorene atom is in a tetravalent state to prevent oxygen deficiency due to reduction. In this embodiment, a layer of oxygen atoms is provided, and Li and- Atomic layer SL1. However, it can provide multiple oxygen atom layers and multiple stone atom layers. In the same way, it can provide multiple nitrogen atom layers called multilayer stone layer atom layers sl2. It can be used as a silicon dioxide with low dielectric constant. If the thickness of the layer is increased below the oxide, then the effect of the oxide with a high K dielectric constant will be reduced. Therefore, there is a limit to the increase in the thickness of the SiO2 film. As for the alternative material of the high-k dielectric film ' It is possible to consider thorium dioxide. However, it is wrong that the semiconductor process causes the material temperature range of the Mata scattered iron type to be shifted. Therefore, it is better to use the titanic oxide to give a phase transition at a higher thorium temperature. Further, high-k dielectric films Other materials include Sr, Ba, Tib L, Ti Y Lr, and oxides of metal elements and oxalates. ♦ Figure 2 shows a sample structure in which the polycrystalline silicon layer 6 is set as the high K formed in the aforementioned manner. Electrodes on the dielectric barrier insulation film. Figures 3 and 4 measure the leakage current characteristics of the sample shown in Figure 2. However, the results shown in Figure 3 indicate that the nitrogen atomic team and team in Figure 1J have been deleted. Take the 4th pattern example as an example, the nitrogen atom layers NLi and NL2 are borrowed from the process of Figures 1D and ^. The ammonia gas heating process of c is formed, and the oxygen atom layer and nitrogen atom layer are formed as The total thickness becomes approximately 1 nanometer. In either case, the hafnium oxide layer < the total film thickness is 3 nanometers. = After the hafnium oxide layer is formed, a rapid heat treatment is performed at 700 C for 30 seconds, and then 59 °. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 \ 297 male sauce) 544735 A7 _ B7 V. Description of the invention (13) Polycrystalline silicon electrode, and then heat treatment at 1000X: 5 seconds, used for dopants Activation heat treatment. In Figures 3 and 4, different curves indicate different blocks. Sample results: Refer to Figure 3, the leakage current density jg at the applied voltage +1 volts is in the range of 0 β to 55 amp centimeters: For other aspects, refer to Figure 4, at the applied voltage + 1 volt, the leakage current density / | In the range of 0.84 to 7.88xl0-5 amp cm · 2, the leakage current is significantly reduced compared to the y graph. Taking the fourth graph as an example, the oxide equivalent thickness is shown ^^ The thickness is 1.77 to 1.84 nm In this way, according to the present invention, by covering the surface of the silicon substrate with an oxygen atom layer, and further covering the upper and lower layers of the high-k dielectric constant layer by the nitrogen atom layer, the high-K dielectric gate insulating layer can be significantly improved. Leakage current characteristics. [First embodiment] FIGS. 5A to 5G show a method of manufacturing a semiconductor device 10 according to a second embodiment of the present invention. Referring to FIG. 5A, a thermal oxidation layer 11a is formed on the silicon substrate 11 having surface directivity (100) ip type by thermal oxidation treatment, and a silicon nitride film 111 is further formed on the thermal oxidation film 11a by CVD. In addition, in the process of FIG. 5A, the silicon nitride film Ub is patterned by dry etching to form an opening corresponding to the isolation region, and the silicon nitride film lb is used as a photomask to apply a dry etching pattern to the thermal oxide film 11a. Another opening of the substrate 11 is formed. In addition, a silicon nitride film lb is used as a photomask to form the isolation grooves 11A and UB having inclined sidewalls, corresponding to the opening formed by exposing the silicon substrate 11 by wet etching. Secondly, in the process of Figure 5B, thermal oxidation is applied to the structure of Figure 5A. The size of the attached paper applies to the Chinese national standard 75) A4 specification ⑵〇χ297mm —-16--

..... install ----- (Please read the precautions on the back before filling this page) Order — 544735 A7 __B7 V. Description of the invention (14) The linear oxide film deleted in the figure is formed in the isolation groove丨 丨 A and 1 side wall and bottom. The isolation trenches 11A and 11B are then filled with a CVD-stone dioxide film. Then, the CVD-SiO2 film, the silicon nitride film 11b below it, and the thermal oxide film Ua below it are grounded and removed by the CMP method to form a silicon dioxide isolation region 11 (: and 110. In the process of FIG. 5B, the surface of the silicon substrate 1 is exposed, and the surface of the silicon substrate is subjected to protective oxidation. Then the protective oxidized surface is removed by hydrofluoric acid treatment to expose the surface of the freshly broken substrate. In the process of FIG. 5C, the processes described in the eighth to eighth diagrams described above to the surface of the silicon substrate 11 are formed to form a gate insulating film 12, and the layer structure is as shown in FIG. 1J. Next is the process of FIG. 5D The polycrystalline stone layer 13 is deposited on the gate insulating film 12, and the same structure as shown in FIG. 2 is obtained. Then, in the process of FIG. 5E, the polycrystalline silicon film 13 and the gate insulating film 12 are patterned to form a polycrystalline silicon gate. 13A, 13B, and 13C. In the process of FIG. 5E, polysilicon gates 13A to 13C are used as photomasks to implant n-type impurities, so LDD expansion regions are formed inside the silicon substrate 11. In particular, LDD expansion regions 14A are formed at the gates. On both sides of the pole 13A, the LDD expansion region HB is formed on the gate 13 On both sides, and the LDD expansion region 14C is formed on both sides of the gate electrode 13C. In the process of FIG. 5E, a sidewall insulating film is formed on each of the gate electrodes 13 A, 13B, and 13C. Gates 13A, 13B, and 13C are used. The side wall film is used as a photomask for ion implantation, so the expanded regions 15A, 15B, and 15C are formed outside the LDD expanded regions 14A, 14B, and 14C. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 17 -------------- · Install --------------------- Order -------------- · Wire. (Please read the notes on the back before filling in this page) 544735 Five Λ invention description (i5) and the process in Figure 5F, such as low-resistance petrified metal layers 13a to 13c and 15a to 15c from silicidation It is formed on the surface of the developed regions 15A to 15C of the gates 13A to 13C by the self-aligned silicide layer method. Finally, in the process of FIG. 5G, the silicon nitride film 16 is formed on the structure of FIG. 5F by cVD. Therefore, the gate electrodes 13 to 13 (:: are covered, and the layer insulating film 17 is further formed on the silicon nitride film 16. Then, the layer insulating film 17 is flattened by the CMP method to form a contact hole, and the contact hole is exposed and unfolded. 15A to 15C, contact plugs 8A to 18C are formed in the contact holes, so they contact the developed regions 15 to 15 respectively. As described, the semiconductor device of the present invention includes a high-κ dielectric gate insulating film formed by the process of FIG. 5C As the gate insulation film 12, a gate insulation film with a short gate length of 1 μm or less and a thickness of 1 to several nanometers is realized. The thickness of the solid film can suppress the gate leakage current caused by the barrier effect. The semiconductor element of this document includes an oxygen atom layer on the gate insulating film i 2 directly connected to the 11th part of the substrate, which constitutes a channel region to achieve stable threshold characteristics, and no dangling bond is formed at the interface between the substrate and the gate insulating film. Interface level. The semiconductor element of the present invention is also used, because the high-W electrical film is sandwiched by a layer of nitrogen atoms, and the metal elements and oxygen of the high-K dielectric film are not spread to the Shi Xi substrate called polycrystalline silicon 3A to 13c, and the result is excellent. Limit characteristics. Further, the dopant impurities from the polycrystalline silicon gate are expanded to the Shixi substrate through the gate insulator, and the fluctuation of the threshold characteristics can be suppressed. In addition, in this specific embodiment, since the nitrogen atom layer is separated from the stone substrate layer by the oxygen atom layer and the stone layer, it can be suppressed due to the fixation of the nitrogen atom and the size of the paper. ^

--------- · Installation: (Please read the precautions on the back before filling out this page)., You can | r line 丨 18 544735 A7 B7 V. Description of invention (16) Threshold characteristics caused by load Ups and downs. Also in this specific embodiment, since the high-K dielectric layer is sandwiched by an oxygen atom layer, the valences of the metal elements such as ytterbium and ytterbium in the high-K dielectric layer are stable, which can prevent, for example, a decrease in relative dielectric constant, etc. problem. [Third Specific Embodiment] Fig. 6 shows a structure of a CMOS semiconductor element 20 according to a third specific embodiment of the present invention. Referring to FIG. 6, the CMOS semiconductor element 20 includes an isolation region 22, which divides the P-type silicon substrate 21 into a p-channel MOS region 20A and an n-channel MOS region 20B. An n-well 20W is formed in the p-channel MOS region 20A. In the p-channel MOS region 20A, a high-K dielectric gate insulating film 23 A having the same layer structure as shown in FIG. 1J is formed, corresponding to the channel region, and a boron-doped polycrystalline silicon gate electrode 24A is formed on the gate insulating film 23 A. . In addition, a silicide metal layer 25A is formed on the polysilicon gate 24 A by a self-aligned silicide layer method. Side wall films are formed on both sides of the polysilicon gate 24A. In the p-channel MOS region 20A, boron ions are implanted into the well 20W to form p-type LDD regions 26Lp corresponding to the sides of the wall surface of the gate 24A. Further, a P + -type expansion region 26p is formed outside the sidewall insulating film. A low-resistance metal layer 27p is formed on the surface of the p + -type development region. Similarly, in the n-channel MOS region 20B, a high-K dielectric gate insulating film 23B having the same layer structure as in FIG. 1J is formed, which corresponds to the channel region; and an arsenic or phosphorus-doped polycrystalline silicon gate 24B is formed in the gate insulation. On film 23B. A self-aligned silicide process is used to form a silicide metal layer 25B on the polysilicon gate 24B. Side wall films are formed on both sides of the polysilicon gate 25B. 19 (Please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 544735 A7 ____B7_ V. Description of the invention (Π) is located in the n-channel MOS area 20B, corresponding to the gate On both sides of the pole 24B wall surface, an n-type LDD region 26Ln is formed by ion implantation of stone or scale, and an n + -type expanded region 26η is further formed on the outside of the sidewall insulation film. A low-resistance metal layer 27n is formed on the surface of the n + -type development region 26n. With this structure of the CMOS device, a p-channel MOS transistor and an n-channel MOS transistor are individually formed to have extremely short gate lengths of 0.1 micrometers or less by using the high-scale dielectric gate insulating film shown in Fig. Υ. Therefore, when the oxide of the gate insulating film is reduced to a film thickness, the insulating films 23A and 23B with a thickness of one to several nanometers can be formed, and the increase of the gate leakage current due to the barrier current can be avoided. In the high κ dielectric gate insulation film of the structure shown in FIG. Ij, since the nitrogen atom layers NLi and NL2 are formed on a thin film, oxygen and metal elements such as thorium and thorium can be effectively suppressed from spreading through the gate insulation films 23A and 23B. And because the high-quality silicon dioxide molecular layer system is formed in the contact silicon channel region, it can avoid the formation of dangling bonds and interface steps at the interface between the silicon substrate and the gate insulation film, and can achieve stable threshold characteristics. Since the nitrogen atom layer NLi is formed separately from the surface of the silicon substrate, it is also possible to avoid fluctuations in threshold characteristics due to the fixed charge of nitrogen atoms. In particular, the CMOS semiconductor device shown in FIG. 6 is used. In the p-channel MOS transistor doped with a polycrystalline silicon gate 24B that is P-type, boron is expanded from the polycrystalline silicon gate 24A to the silicon substrate 21 by forming nitrogen atom layers NL1 and NLjip. It can avoid the fluctuation of the threshold characteristics caused by the doping of the channel region. In addition, the present invention is not limited to these specific embodiments, and various changes and modifications can be made without departing from the scope of the present invention. This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 > < 297). 20 Gutter · (Please read the precautions on the back before filling this page) 544735 A7 B7 V. Invention Description (i8) Element reference number 1 ... Dream substrate 3 ... Nitride layer 10 ... Semiconductor element 11 a ... Thermal oxide film 11A, 11B ... Isolation trench 12 ... Gate insulating film 13a-c ... Silicon metal layer 14A-C ·· DD development area 15A-C ... development area 17... Layer insulation film 20... CMOS semiconductor element 206......... 23 Α · B ··· South K dielectric gate insulation film 25 AB ··· Shixihua metal layer 26Lp ... p-type LDD region 26P ··· ρ + -type expansion region 2 ---- oxidized fragmentation layer 6 ··· Polycrystalline layer 11 · ._ρ-type silicon substrate 11 b ··· Nitride chip lie, 11D ··· Silicon dioxide barrier 13 .. .Polycrystalline layer 13 A-C ... Polycrystalline layer Electrode 15a_c ... silicided metal layer 16 ... nitride nitride film 18A-C ... contact plug 20A ... ρ channel MOS region 20W " .n-type well 22 ... isolation region 2 4 A-B ... polycrystalline seconds Interrogator 26Ln ._. N-type LDD region 26η ·· .n + -type expansion region 27p ··· Shi Xihua Metal Low Current Floor

Claims (1)

544735 patent claim range 2. 4. 6. 8. A semiconductor device includes: a channel region formed in the crystal layer of the stone, a gate insulating film formed in the channel region, containing a silicon oxide layer formed on silicon On the crystal layer, a first nitride layer formed on the silicon oxide layer, a dielectric metal oxide layer formed on the first nitride layer, and a first metal nitride layer formed on the silicon nitride layer. A layer of dinitride and a gate are formed on the gate insulating film. For example, the semiconductor device according to claim w, wherein the oxide layer includes an oxygen atom layer, which uniformly covers the surface of the silicon substrate. For example, the semiconductor device according to claim 2 in which the oxygen atomic layer is a single atomic layer of oxygen. Such as the scope of patent application! The semiconductor device according to claim 1, wherein the first silicon nitride layer includes a nitrogen atom layer 'which uniformly covers the surface of the silicon oxide layer. For example, if you apply for the semiconductor device of item 2, the nitrogen atomic layer of the first nitride layer is a nitrogen monoatomic layer. = The semiconductor device under the scope of patent application No. 2 in which 9q% or more of the oxygen atomic layer of the oxidized oxidized layer of the oxygen atomic layer is atomically bonded to the surface of the primary crystal layer. For example, for the semiconductor device under the scope of patent application No. 4, 90% or more of the nitrogen material of the nitrogen material layer of hafnium nitride is bonded with an oxygen atom. On the evening of the patent application scope! In terms of semiconductor devices, the M brother—the nitrided nitride layer and the second nitrided nitride layer are each approximately】 molecule layers ^ thick (Please read the notes on the back before filling out this page) • Order-、 Scope of patent application. 9 ·: The semiconductor device No. W in the patent application range, wherein the surface of the dielectric metal .7 compound layer is uniformly covered by an oxygen atom layer composed of oxygen atoms. The semiconductor device according to item 1 of the patent application scope, wherein the second silicon nitride layer includes a nitrogen atom layer uniformly covering the dielectric metal oxide layer. For example, the semiconductor device in the scope of the patent application, wherein the nitrogen atom layer of the silicon dinitride layer is a nitrogen single atom layer. 12. For a semiconductor device as claimed in item 9 of the patent application, wherein the gas atoms of the rat atomic layer of the second nitride layer are mainly bonded to the oxygen atoms of the oxygen atom layer covering the surface of the dielectric metal oxide layer. 13. For example, the oldest semiconductor element in the scope of patent application, in which the dielectric metal oxygen layer is an oxygen atom layer of oxygen atoms and a metal atom layer of metal atoms. The parent replacement layer is formed as a laminate, and each layer is a single atom thickness. The semiconductor element according to the scope of the patent application of M. ^, wherein the dielectric metal oxide layer is an oxidation of a metal element selected from the group consisting of Zr, Hf, Sr, Ba, Ta, Ti, γ, Lr, and lanthanide. And silicate. 15. The semiconductor device according to claim w, wherein the gate is composed of polycrystalline stone. 16. A semiconductor element comprising: a Shi Xi substrate, a gate insulating film formed on a silicon substrate; and a gate electrode formed on the gate insulating film, wherein the gate insulating film includes: a first insulating film including An oxygen atom consisting of oxygen atoms This paper is sized to the Chinese National Standard (CNS) A4 specification (21〇 > < 297) • Order 丨 (Please read the precautions on the back before filling this page) VI. Patent application scope Each oxygen atomic layer on the surface of Shixi substrate is bonded to Shixi atomic layer · —Shixi atomic layer composed of Shixi atoms, each The Shixi atomic system is bonded to the oxygen atom of the oxygen atomic layer; the nitrogen atomic layer consisting of one nitrogen atom 'each nitrogen atomic system is bonded to the Shixi atomic layer of the Shixi atomic layer; and the second Shixi atom is composed of one Shixi atomic layer Layer, each Shixi atomic system is bonded to the nitrogen atom of the nitrogen atom layer, a second insulating plutonium, which contains an oxygen atom layer composed of oxygen atoms, and each of the oxygen atomic systems is bonded to the second plutonium layer. A metal atomic layer composed of metal atoms, each metal atom being an oxygen atom bonding of a disk oxygen atomic layer; an oxygen atomic layer consisting of an oxygen atom, each milk atomic system being bonded to a metal atomic metal atomic layer; and Topmost ... The topmost oxygen atomic layer composed of oxygen atoms is bonded to one metal atom of the metal atomic layer, and the atom-third insulating film includes a stone-cut atomic layer composed of -cut atoms, and this layer covers the most On top of the oxygen atom layer, each Shixi atomic layer is bonded to an oxygen atom on the top page of the oxygen atom layer; and a layer consisting of nitrogen atoms: = layer, each nitrogen atom system and the topmost oxygen atom layer and silicon atom layer , A silicon atom bond. 17. A compensating semiconductor device comprising a silicon substrate having a first device region of a first conductivity type, a second device region of a second conductivity type, and a second region insulated by a first region of an isolation region. The film is formed on the first element region of the Shixi substrate-the gate insulation film. It is formed on the second element region of the ⑪ substrate-the first and the inter-pole electrodes are formed on the first insulating film. The second opening is formed on the second insulating film, the space, the edge film and the second insulating film each contain ..., and the younger bank: the second insulating film, which contains-an oxygen atom consisting of oxygen atoms. The atomic bond of the milk atomic system and the surface of the hair cutting board is a stone Xiyuan ::: Dream atomic layer, each of the atomic layer and the oxygen atomic layer of oxygen and _ of === the second atomic layer of each nitrogen atomic system, each The ㈣ atomic system is bonded to the nitrogen atom of the nitrogen atom layer, each layer:;: The edge 臈 contains an oxygen atom composed of oxygen atoms: the u system is bonded to the silicon atom of the second silicon atom layer, and the mongolian atom A metal atomic layer composed of oxygen atomic bonds of each gold atomic layer; oxygen atoms composed of oxygen atomic layers Layer 1 milk atom system is bonded with metal atom of metal atom layer, and at the top, a top oxygen atom layer composed of oxygen atoms, each oxygen atom system is bonded with one metal atom of metal atom layer, and A silicon atom layer, a silicon atom bonded to a three-layer insulation film 'contains a stone evening atomic layer composed of stone evening atoms' This layer covers the topmost oxygen atomic layer, and each stone evening atomic layer is connected to the topmost oxygen atomic layer. An oxygen atom bond; and a nitrogen atom layer composed of nitrogen atoms, each nitrogen atom system covering a topmost oxygen atom layer, and a method for manufacturing a semiconductor device, including: (A)-a process in which gas phase silicon is supplied to The surface of the silicon substrate allows the surface of the silicon substrate to absorb silicon molecules of a single molecular thickness. (B) —The process in which oxygen-containing gas is supplied to the surface of the silicon substrate. The table 18. 544735 A8 B8 C8 D8 6. The scope of patent application is in the process (A ) Later absorb silicon atoms, so the adsorbed silicon molecules are oxidized to produce a molecular layer of stone oxide on the surface of the stone substrate. (C) A process in which gas-phase silicon is supplied to the surface of the silicon substrate The surface is covered by a silicon oxide molecular layer after the process (B), so the silicon molecules are absorbed to a single molecular thickness, (D) — the process in which a nitrogen-containing gas is supplied to the surface of the silicon substrate, and the surface is after the process (C) Adsorption of silicon molecules, allowing the adsorbed silicon molecules to form a silicon nitride molecular layer on the surface of the silicon substrate, (E)-process, in which oxygen-containing gas and metal element-containing gas are alternately supplied to the surface of the silicon substrate, which surface is after the process (D) It is covered by a silicon nitride molecular layer, thereby forming a dielectric metal oxide film, (F)-a process in which fumed stone is supplied to the substrate surface, and the surface needs to be covered by the dielectric metal oxide film after the process (E) Therefore, Shi Xi molecules are adsorbed to a single-molecule thickness to form a Shi Xi molecular layer, and (G)-a process in which a nitrogen-containing gas is supplied to the substrate surface, and the surface is covered by a silicon molecular layer after the process (F), so it is The adsorbed silicon molecules form a silicon nitride molecular layer on the surface of the silicon substrate. 19. The method for manufacturing a semiconductor device according to item 18 of the scope of patent application, wherein the process (E) starts from a process in which an oxygen-containing gas is supplied to a surface of a silicon substrate, and finally a process in which an oxygen-containing gas is supplied to a surface of a silicon substrate. 26 (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)